JP5617903B2 - Vehicle wires, vehicle cables - Google Patents

Description

The present invention relates to a flame-retardant non-halogen resin composition, a vehicle electric wire coated with the resin composition, and a vehicle cable having the electric wire.

  Conventionally, as a flame-retardant non-halogen resin composition used for insulated wires and cables, a resin composition obtained by adding a surface-treated or untreated metal hydroxide such as magnesium hydroxide to a polyolefin-based resin (For example, refer to Patent Documents 1 to 3).

  Since these flame retardant resin compositions do not contain halogen compounds, no toxic gases such as hydrogen chloride and toxic substances such as dioxins are generated during combustion. It is said that there is no problem even if it is incinerated at the time of disposal.

  On the other hand, in the production of these non-halogen flame retardant resin compositions, in order to improve the flame retardancy, it is generally performed to add a large amount of the above-mentioned metal hydroxide, which is a non-halogen flame retardant, to polyolefin. Yes.

JP 2000-129049 A JP 2000-178386 A JP 2000-195336 A

  However, when the above metal hydroxide is highly filled in order to improve flame retardancy, the shear viscosity of the resin composition increases, and the torque during extrusion increases, so it is necessary to reduce the linear speed and produce Sex is reduced. Further, when the filling amount of the metal hydroxide is increased, the mechanical properties are deteriorated, and there is a problem that a target electric wire cannot be obtained.

  In particular, in the case of electric wires and cables for vehicles, oil resistance and cold resistance are also required to be excellent, and it is necessary to satisfy these characteristics.

Accordingly, an object of the present invention is to provide a vehicle electric wire that is coated with a non-halogen resin composition that has high flame retardancy, has low viscosity, can prevent an increase in torque during extrusion, and has excellent tensile properties, and It is providing the cable for vehicles which has the said electric wire. In addition to the above properties, in particular provides suitably used may oil resistance and cold resistance excellent non-halogen resin composition coated wire vehicle as wire and cable for a vehicle, and a vehicle cable having the electric wire There is.

In order to achieve the above object, the present invention provides the following electric wires for vehicles and cables for vehicles according to [1] to [8].

[1] An electric wire for a vehicle in which a conductor is covered with an insulator, the insulator being 100 to 250 parts by mass of a metal hydroxide with respect to 100 parts by mass of a polyolefin-based resin as a base polymer. The polyolefin resin comprising 3 to 50 parts by mass of silica, the amorphous silica comprising a non-halogen resin composition having a specific gravity of 2.1 to 2.3 g / cm ^{3 and} a specific surface area of 15 to 50 m ² / g. Is a maleic anhydride-modified ethylene-α-olefin copolymer of 10 to 40% by mass, a melt mass flow rate (MFR) of 2.0 (g / 10 min) or less, and a density of 0.900 to 0.925 g / cm ³ . The electric wire for vehicles characterized by including 60-90 mass% of polyethylene .
[2] A vehicle cable having an electric wire in which a conductor is covered with an insulator and a sheath covering the electric wire, wherein the sheath is metal hydroxide with respect to 100 parts by mass of a polyolefin-based resin as a base polymer. 100 to 250 parts by mass of the product, 3 to 50 parts by mass of amorphous silica, and the amorphous silica has a specific gravity of 2.1 to 2.3 g / cm ^{3 and} a specific surface area of 15 to 50 m ² / g. Comprising a non-halogen resin composition , the polyolefin resin is a maleic anhydride-modified ethylene-α-olefin copolymer of 10 to 40% by mass, a melt mass flow rate (MFR) of 2.0 (g / 10 min) or less, a density A vehicle cable comprising 60 to 90% by mass of polyethylene of 0.900 to 0.925 g / cm ³ .

ADVANTAGE OF THE INVENTION According to this invention, the electric wire for vehicles by which the non-halogen resin composition which was highly flame-retardant, was low-viscosity, can prevent the torque increase at the time of extrusion, and was excellent in the tensile characteristic was covered, and the said electric wire It is possible to provide a vehicle cable having the following. In addition to the above properties, in particular provides suitably used may oil resistance and cold resistance excellent non-halogen resin composition coated wire vehicle as wire and cable for a vehicle, and a vehicle cable having the electric wire be able to.

It is sectional drawing of the electric wire coat | covered with the non-halogen resin composition which concerns on embodiment of this invention. It is sectional drawing of the cable which has the electric wire of FIG. 1 which concerns on embodiment of this invention.

(Non-halogen resin composition)
The non-halogen resin composition used in the present invention contains 100 to 250 parts by mass of a metal hydroxide and 3 to 50 parts by mass of amorphous silica with respect to 100 parts by mass of a polyolefin-based resin as a base polymer. Crystalline silica has a specific gravity of 2.1-2.3 g / cm ^{3 and} a specific surface area of 15-50 m ² / g.

Examples of the polyolefin resin in the present embodiment include low density polyethylene, linear low density polyethylene, linear ultra-low density polyethylene, maleic acid grafted linear low density polyethylene, ethylene-methyl methacrylate copolymer, ethylene-methyl. Acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-styrene copolymer, maleic anhydride modified ethylene-α-olefin copolymer, ethylene-propylene copolymer, It is preferable to use at least one selected from the group consisting of an ethylene-butene copolymer, an ethylene-octene copolymer, and a graft polymer of these and vinylsilane. Among these, from the viewpoint of oil resistance and cold resistance, an ethylene-α-olefin copolymer modified with maleic anhydride and a melt mass flow rate (MFR) of 2.0 (g / 10 min) or less, and a density of 0.900 to 0.00. 925 g / cm ³ of polyethylene (polyethylene refers to low-density polyethylene, linear low-density polyethylene, linear ultra-low density polyethylene, or maleic acid grafted linear low-density polyethylene; the same shall apply hereinafter). It is more preferable to use at least one selected from the group. It is particularly preferable to use a maleic anhydride-modified ethylene-α-olefin copolymer and polyethylene having an MFR of 2.0 (g / 10 min) or less and a density of 0.900 to 0.925 g / cm ³ .

When the MFR of polyethylene is more than 2.0 g / 10 min, the molecular weight is small and the oil resistance is lowered. Further, when the density of polyethylene is less than 0.900 g / cm ³ , the amount of crystals is not sufficient and the oil resistance decreases, and when it exceeds 0.925 g / cm ³ , the amount of crystals increases and the elongation decreases.

  The maleic anhydride-modified ethylene-α-olefin copolymer is preferably added so as to be contained in an amount of 10 to 40% by mass based on the total amount of the polyolefin resin as the base polymer. If the amount is less than 10% by mass, the adhesion between the polymer, the metal hydroxide and the amorphous silica is not sufficient, and the cold resistance is lowered. If the amount exceeds 40% by mass, the adhesion becomes strong and the elongation is lowered.

The polyethylene having an MFR of 2.0 (g / 10 min) or less and a density of 0.900 to 0.925 g / cm ³ is preferably added so as to be contained in an amount of 60 to 90% by mass with respect to the total amount of the polyolefin resin as the base polymer. . If the amount is less than 60% by mass, the amount of crystals is insufficient and the oil resistance is lowered, and if it exceeds 90% by mass, the amount of crystals increases and the elongation decreases.

  Examples of metal hydroxides that can be suitably used in the present embodiment include those metal hydroxides in which magnesium hydroxide, aluminum hydroxide, calcium hydroxide, and nickel are dissolved. These may be used alone or in combination of two or more. In addition, these metal hydroxides may be used which are surface-treated with a silane coupling agent, a titanate coupling agent, a fatty acid such as stearate or calcium stearate, a fatty acid metal salt, or the like. Further, an appropriate amount of metal hydroxide other than these may be added.

  100 to 250 parts by mass of the metal hydroxide is added as a flame retardant with respect to 100 parts by mass of the polyolefin-based resin as the base polymer. When the addition amount is less than 100 parts by mass, sufficient flame retardancy cannot be obtained, and when it is more than 250 parts by mass, the mechanical properties are deteriorated. The addition amount of the metal hydroxide is preferably 130 to 220 parts by mass, and more preferably 150 to 200 parts by mass.

The amorphous silica that can be used in this embodiment has a specific gravity of 2.1 to 2.3 g / cm ^{3 and} a specific surface area of 15 to 50 m ² / g. By using the amorphous silica, the effects of the present invention can be achieved. The specific gravity of the amorphous silica is preferably 2.15 to 2.25 g / cm ³ , and the specific surface area is preferably 30 to 50 m ² / g.

  Amorphous silica is added as a flame retardant aid in an amount of 3 to 50 parts by mass with respect to 100 parts by mass of a polyolefin resin as a base polymer. When the addition amount is less than 3 parts by mass, sufficient flame retardancy cannot be obtained, and when it is more than 50 parts by mass, the mechanical properties are significantly deteriorated. The amount of amorphous silica added is preferably 3 to 30 parts by mass, and more preferably 5 to 20 parts by mass.

  In addition to the above flame retardants and flame retardant aids, as long as they do not impair the properties of the present invention, antioxidants, lubricants, softeners, plasticizers, inorganic fillers, compatibilizers, stabilizers, Additives such as carbon black and colorants can be added. In order to further improve the performance, flame retardants and flame retardant aids other than the above flame retardants and flame retardant aids may be added as long as the characteristics of the present invention are not impaired.

The non-halogen resin composition used in the present invention is preferably crosslinked. By performing crosslinking, the mechanical properties of the resulting resin composition are improved. As the cross-linking method, an electron beam cross-linking method in which an electron beam is irradiated after molding, or chemical cross-linking in which a cross-linking agent is previously blended in the resin composition and then heated and cross-linked is employed.

  The non-halogen resin composition according to a preferred embodiment of the present invention has a low viscosity at the time of extrusion, excellent workability, and excellent flame retardancy, mechanical properties, oil resistance, and cold resistance, and therefore, automotive parts, tubes, adhesives, and building materials. It can be used widely.

(Electric wires and cables)
FIG. 1 is a cross-sectional view of an electric wire coated with a non-halogen resin composition according to an embodiment of the present invention. Moreover, FIG. 2 is sectional drawing of the cable which has the electric wire of FIG. 1 which concerns on embodiment of this invention.

  An electric wire 10 shown in FIG. 1 is an electric wire in which a conductor 1 made of copper is coated with an insulator 2 made of a non-halogen resin composition according to an embodiment of the present invention. The thickness of the insulator 2 is preferably 0.1 to 1.5 mm, and more preferably 0.3 to 1.2 mm.

  The electric wire 10 according to the embodiment of the present invention is not limited to a single insulating layer, and may be provided in multiple layers as long as the effects of the present invention are exhibited, and include other intermediate layers. May be.

  On the other hand, the cable 20 shown in FIG. 2 is provided with a tape layer 3 such as a resin tape (PET tape or the like) on the outer periphery of a two-wire core in which two electric wires 10 shown in FIG. After the metal layer 4 and the tape layer 3 are formed, the outermost periphery is covered with the sheath 5 made of the non-halogen resin composition according to the embodiment of the present invention.

  In addition, in the cable 20 in which the sheath 5 is made of the non-halogen resin composition according to the embodiment of the present invention, an electric wire coated with the insulator 2 that does not use the non-halogen resin composition according to the embodiment of the present invention is used. You can also.

  The electric wires and cables according to preferred embodiments of the present invention do not generate toxic gas during combustion, and have high flame retardancy, excellent mechanical properties, oil resistance, and cold resistance.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited only to these examples.

The electric wires of Examples , Reference Examples and Comparative Examples were produced as follows.
Each component was blended according to the blending shown in Table 1 and Table 2, and kneaded at a start temperature of 40 ° C. and an end temperature of 200 ° C. by a 25 liter pressure kneader, and then pelletized. Using a 65 mm extruder, the produced pellets were extrusion molded onto a conductor having an outer diameter of 1.1 mm with an insulator coating thickness of 0.7 mm at a set temperature of 200 ° C. After extrusion coating, irradiation cross-linking was performed with 7 Mrad to produce an electric wire.
The electric wires were evaluated by the method shown below. The evaluation results are shown in Tables 1 and 2.

(1) Tensile test A tensile test was performed on the produced electric wires in accordance with EN60811-1-1. The tensile strength was 10 MPa or more, and the elongation was 150% or more.

(2) Flame Retardancy Test The manufactured wires were subjected to a vertical combustion test according to EN60332-1-2. In the judgment, after extinguishing, the case where the distance between the lower end of the upper support material and the carbonization start point was less than 50 mm was regarded as unacceptable (x), and the case where the distance was 50 mm or more was regarded as acceptable (◯).

(3) Viscosity test The viscosity of the kneaded pellets was measured using a Capillograph 1B manufactured by Toyo Seiki Seisakusho. The viscosity was measured when a pellet was extruded from a capillary having a length of 5.0 mm and an outer diameter of 1.0 mm at a measurement temperature of 200 ° C. and a shear rate of 6.1 × 10 ³ sec ⁻¹ . Those having a viscosity of less than 270 Pa · s were accepted (◯), and those having a viscosity of 270 Pa · s or more were judged to be unacceptable (x).

(4) Oil resistance test In accordance with EN60811-1-3, the prepared electric wire was immersed in oil IRM902 for oil resistance test, heated in a thermostatic bath at 100 ° C for 72 hours, left at room temperature for about 16 hours, and subjected to a tensile test. It implemented and evaluated by the value (residual rate) after oil immersion heating with respect to the initial value. The residual tensile strength was 70% or more as acceptable (◯), and the residual elongation was 60% or more as acceptable (◯).

(5) Cold resistance test The produced wires were subjected to a low temperature bending test at -40 ° C in accordance with EN60811-1-4 8.1. The thing which the crack generate | occur | produced at the time of a bending was made disqualified (x), and the thing in which the crack did not generate | occur | produced was made into pass ((circle)).

(6) Comprehensive judgment All the tensile tests, flame retardant tests, viscosity tests, oil resistance tests, and cold resistance tests are acceptable (◎), and all of the tensile tests, flame retardant tests, and viscosity tests are acceptable. However, if either of the oil resistance test or the cold resistance test fails, it is judged as good (○), and if any of the tensile test, flame retardancy test, or viscosity test is rejected, it is judged as bad (×). .

[Materials used]
(Base polymer)
Polymer A (linear low density polyethylene): (trade name) Evolue SP1510, manufactured by Prime Polymer Co., Ltd., density: 0.915 g / cm ³ , MFR: 1.0 g / 10 min
Polymer B (linear low density polyethylene): (trade name) Evolue SP2030, manufactured by Prime Polymer Co., Ltd., density: 0.922 g / cm ³ , MFR: 2.5 g / 10 min
Polymer C (maleic anhydride modified ethylene-α-olefin copolymer): (trade name) Toughmer MH5040, manufactured by Mitsui Chemicals, Inc. Polymer D (ethylene-vinyl acetate copolymer): (trade name) Evaflex 45X, manufactured by Mitsui DuPont Polychemical Co., Ltd., Polymer E (ethylene-ethyl acrylate copolymer): (trade name) Lexpearl A1150, manufactured by Nippon Polyethylene Co., Ltd.
(Evolue, Tuffmer, Everflex and Lexpearl are registered trademarks)

(Flame retardants)
Magnesium hydroxide: (trade name) Magseeds S4, manufactured by Kamishima Chemical Co., Ltd. (Magseees is a registered trademark)
(Flame retardant aid)
Amorphous silica A: (trade name) SIDISTAR T120U, manufactured by Elchem Japan KK, specific gravity 2.2 g / cm ³ , specific surface area 40 m ² / g
・ Crystalline silica: (trade name) Aerosil R972, manufactured by Nippon Aerosil Co., Ltd. ・ Amorphous silica B: (trade name) Vulkasil A-1, manufactured by Bayer Co., Ltd., specific gravity 2.0 g / cm ³ , specific surface area 65m ² / g
Amorphous silica C: (trade name) Durosil, manufactured by Degussa Co., Ltd., specific gravity 2.1 g / cm ³ , specific surface area 60 m ² / g

(Crosslinking aid)
・ Trimethylolpropane trimethacrylate: (trade name) TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd. (antioxidant)
Antioxidant A: (trade name) ADK STAB AO-18, manufactured by ADEKA Corporation (ADK STAB is a registered trademark)
Antioxidant B: (trade name) Irganox 1010, manufactured by BASF, (IRGANOX is a registered trademark)
(Lubricant)
・ Zinc stearate: (trade name) EZ101, manufactured by Katsuta Chemical Co., Ltd. (colorant)
・ Carbon black: (trade name) Asahi Thermal FT, Asahi Carbon Co., Ltd. (Asahi Thermal is a registered trademark)

In Examples 1 to 9, all of the tensile test (tensile strength and elongation), the flame retardancy test (vertical combustion test), the viscosity test, the oil resistance test, and the cold resistance test were passed, and good characteristics were exhibited. Further, although Reference Examples 1 to 3 failed the oil resistance test or the cold resistance test, they exhibited good characteristics in a tensile test (tensile strength and elongation), a flame retardancy test (vertical combustion test), and a viscosity test.

On the other hand, in Comparative Example 1, the amount of magnesium hydroxide added was 95 parts by mass, less than 100 to 250 parts by mass, which is the range of the present invention, and the flame retardancy was insufficient. On the contrary, in Comparative Example 2, the amount of magnesium hydroxide added was 255 parts by mass, more than 100 to 250 parts by mass, which is the range of the present invention, and the elongation was insufficient.
In Comparative Example 3, the amount of amorphous silica added was 2 parts by mass, less than 3 to 50 parts by mass which is the range of the present invention, and the flame retardancy was insufficient. On the contrary, in Comparative Example 4, the amount of amorphous silica added was 55 parts by mass, more than 3 to 50 parts by mass which is the range of the present invention, and the elongation was insufficient.
In Comparative Example 5, crystalline silica was used, the viscosity was high, the formation of the carbonized layer was small, and the flame retardancy was insufficient. In Comparative Example 6, amorphous silica having a specific gravity of 2.0 is used, which is less than 2.1 to 2.3 g / cm ³ which is the range of the present invention, formation of a carbonized layer is small, and flame retardancy is low. It was insufficient. In Comparative Example 7 the specific surface area and is used amorphous silica of 60 m 2 / ^g, more than 15 to 50 m 2 / ^g is in the range of the present invention, was insufficient higher viscosity.

10: electric wire, 1: conductor, 2: insulator 20: cable, 3: tape layer, 4: metal layer, 5: sheath

Claims (2)

A vehicle electric wire with a conductor covered with an insulator,
The insulator includes 100 to 250 parts by mass of a metal hydroxide and 3 to 50 parts by mass of amorphous silica with respect to 100 parts by mass of a polyolefin-based resin as a base polymer. A non-halogen resin composition having a specific gravity of 1 to 2.3 g / cm ^{3 and} a specific surface area of 15 to 50 m ² / g ,
The polyolefin resin is a maleic anhydride-modified ethylene-α-olefin copolymer of 10 to 40% by mass, a melt mass flow rate (MFR) of 2.0 (g / 10 min) or less, and a density of 0.900 to 0.925 g. The electric wire for vehicles characterized by including 60-90 mass% of polyethylene of / cm < ³ > . An electric wire with a conductor coated with an insulator;
A vehicle cable having a sheath covering the electric wire,
The sheath includes 100 to 250 parts by mass of a metal hydroxide and 3 to 50 parts by mass of amorphous silica with respect to 100 parts by mass of a polyolefin-based resin as a base polymer. A non-halogen resin composition having a specific gravity of ˜2.3 g / cm ^{3 and} a specific surface area of 15-50 m ² / g ,
The polyolefin resin is a maleic anhydride-modified ethylene-α-olefin copolymer of 10 to 40% by mass, a melt mass flow rate (MFR) of 2.0 (g / 10 min) or less, and a density of 0.900 to 0.925 g. A cable for a vehicle comprising 60 to 90% by mass of polyethylene of / cm ³ .

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